2-氧代-2-[(2-氯-5-吡啶甲氨基)(芳基)甲基]-4-芳基-5,5-二甲基-1,3,2-二氧膦杂环己烷的合成及其生物活性研究

通过类Mannich 反应“一锅法”合成了10个未见文献报道的含吡啶基的环状α-氨基膦酸酯, 其结构经¹H NMR, ³¹P NMR, IR, MS和元素分析确证. 测定了该系列化合物的杀虫、杀菌和除草活性, 结果表明, 所测化合物的杀虫活性不太好, 但所有化合物在药液浓度为1.0×10^－4 g/mL 时都具有较好的除草活性, 部分化合物在5.0×10^－5 g/mL时显示出良好的杀菌活性.     

Syntheses of polyfluoroalkyl aryl ether

The reactions of methoxyphenol and dihydroxybenzene with hexafluoropropene were studied. Eight new compounds 2-9 were separated from the reaction mixture of catechol and hexafluoropropene. The formation of these products was explained through nucleophilic attack of the aryloxy anion on hexafluoropropene, followed by elimination and addition (Scheme 1). However, the reaction of resorcinol and hydroquinone with C₃F₄ only gave the simple addition products 10 and addition-elimination products Z, E-11, 12. All new compounds were characterized by ¹H and ¹⁹F NMR, IR, MS and elemental analyses. The ¹⁹F NMR of seven membered ring compounds 4 and 5 were discussed in detail.     

酰基硫脲衍生物的合成、结构表征及生物活性研究

在超声波辐射下, 以PEG-400为固-液相转移催化剂, 用芳胺与双酰基异硫氰酸酯反应, 合成出了15种新的结构不对称的双酰基硫脲类化合物(6和6')和9种新的分子中含酰胺基团的单酰基硫脲类化合物(7和7'). 利用元素分析, IR, ¹H NMR, ¹³C NMR, APT, 1D NOE及2D NMR技术确定了所合成化合物6和6'及7和7'的结构, 并对它们NMR谱中低场C, H进行了归属. 杀菌、杀虫和除草活性筛选测定实验结果表明, 所测试化合物对瓜炭疽病菌均具有抑制作用, 其中6e抑制率最高, 达到62.4%; 目标化合物7a对黄瓜白粉病菌有一定的抑制作用. 单胺氧化酶活性测定实验表明：大部分目标化合物对单胺氧化酶具有一定的抑制活性, 其中浓度在1×10^－3 mol•L^－1时目标化合物6'c和6'd的抑制活性较强, 明显高于其它化合物. 目标化合物没有抗惊厥活性.     

穿心莲中两个黄酮苷的波谱学研究

研究了穿心莲中抗血栓的活性成分. 应用AB-8大孔吸附树脂、聚酰胺柱色谱及薄层色谱进行分离, 应用波谱学(¹H NMR, ¹³C NMR, DQFCOSY, TOCSY, HMQC, HMBC, NOESY等)方法进行结构鉴定. 分离得到两个黄酮苷类化合物, 确定了¹H NMR, ¹³C NMR信号的全归属. 化合物1鉴定为5,4'-二羟基-7-甲氧基黄酮-6-O-β-D-葡萄糖苷, 化合物2鉴定为5,4'-二羟基-7-甲氧基黄酮-8-O-β-D-葡萄糖苷, 化合物1为首次从该植物中分得, 首次对两个化合物的碳谱和氢谱进行了全归属.     

Synthesis and Insecticidal Evaluation of Novel N‐Pyridylpyrazolecarboxamides Containing Different Substituents in the ortho‐Position

In order to look for novel insecticides containing N‐pyridylpyrazole, ten novel pyrazolecarboxamides containing different ortho‐substituents in the aniline part were synthesized, and their structures were characterized by ¹H NMR, ¹³C NMR and HRMS. The single crystal structure of 10b was determined by X‐ray diffraction. Their evaluated insecticidal activity against oriental armyworm (Mythimna separata) indicated that all the compounds exhibited moderate insecticidal activities.     

Reactions of pentachloro-2-nitrobutadiene with some aliphatic and heterocyclic thiols and a crystallographic study

In this study, S-, S,S- and S,O-substituted novel nitrodiene compounds were synthesized. Cyclization products were formed when difunctional nucleophiles were used. The stereoisomerism of a heterocyclic nitrodiene is discussed with the help of XRD studies. The structures of all compounds were characterized by spectroscopic methods (FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, MS) and microanalysis.     

A Convenient Synthesis and Biological Research of Novel 5,6,7,8‐Tetrahydro‐1,6‐naphthyridin‐2(1H)‐one Derivatives Hydrochloride as Cytotoxic Agents

A series of 5,6,7,8‐tetrahydro‐1,6‐naphthyridin‐2(1H)‐one derivatives hydrochloride were obtained using a convenient and mild method from 4‐piperidone monohydrate hydrochloride. The newly synthesized compounds and their derivatives were characterized by ¹H NMR, ¹³C NMR, and high‐resolution mass spectrometry. Furthermore, cytotoxicity in vitro of the synthesized compounds were screened using MTT or CCK8 assay. The results showed that some of the compounds showed potential antitumor activity. Among of them, compound 10a had effects against tumor cells (MOLM‐13), and the half maximal inhibitory concentration value was 76 μmol/L.     

硫（醇）代N-对甲苯基/苯基磺酰基氨基羧酸酯类化合物的合成与神经营养活性

根据官能团的组合,设计合成了硫（醇）代N-对甲苯基/苯基磺酰基氨基羧酸酯类化合物,这些化合物的结构¹H NMR, ¹³C NMR, MS 和 HRMS证实,初步的实验结果表明：在10μg/mL浓度下,化合物4a, 4b, 4d, 5c, 5d, 5g, 6b和 6d显示对PC12细胞缺氧损伤具有显著的保护作用,化合物4c, 5b和 6c显示对PC12细胞缺氧损伤具有一定的保护作用;在5μg/mL浓度下,4d和 6d显示对PC12细胞缺氧损伤具有一定的保护作用;初步的实验也表明：在10μg/mL浓度下,4c, 5a, 5c, 5d, 5e和 6b显示对PC12细胞具有一定的促分化作用。     

Antitubercular Activity and Synergistic Study of Novel Pyrazole Derivatives

A series of 20 novel pyrazole derivatives were designed and prepared, characterized by ¹H‐NMR, mass spectra (ES‐MS), ¹³C‐NMR, and elemental analysis. The synthesized compounds were then evaluated for their growth inhibitory activity against Mycobacterium smegmatis mc² 155 initially. Rifampicin was used as standard reference. In this screening, derivatives 9 , 10 , and 11 presented superior inhibition compared with standard. Later, these three compounds were exposed for their Mycobacterium tuberculosis H37Rv inhibitory assay using rifampicin as standard reference. Encouraging M. smegmatis mc² 155 inhibition (9 μg/mL), M. tuberculosis H37Rv inhibition (1.9 μg/mL), and synergism with the first‐line and second‐line antibiotics made compound 10 as lead and safe antitubercular agent among the series.     

The Synthesis,Spectral, and Electrochemical Characterization of Novel Alkoxybenzoquinone Derivatives

The novel monosubstituted benzoquinone compounds 3e , 3g , 3h ; 2,5‐O‐ substituted benzoquinone compounds 4a , 4b , 4c , 4d , 4e 4g and known compound 4h and 2,6‐O‐ substituted benzoquinone compounds 5e , 5f , 5g , 5h were obtained by the reaction of p‐chloranil ( 1 ) and related alcohol compounds in potassium carbonate (K₂CO₃) solution of acetonitrile or chloroform with Et₃N. The novel cyclic compounds 7 , 8 and 10 , 11 were obtained from the reaction of p‐chloranil ( 1 ) and diols in potassium carbonate (K₂CO₃) solution of acetonitrile at room temperature. The structures of novel compounds were characterized by using micro analysis, FT‐IR, ¹H‐NMR, ¹³C‐NMR, MS and cyclic voltammetry.     

Design,synthesis, and anticancer activities of sodium quinazolin-4-diselenide compounds

Substituted 4-chloroquinazoline reacted with sodium diselenide to give novel sodium quinazoline-4-diselenide compounds. The reaction provides an efficient and facile approach to the synthesis of sodium quinazoline-4-diselenide compounds. Structures of title compounds were confirmed by IR, ¹H NMR, ¹³C NMR, and elemental analysis. MTT assay was adopted to show anticancer activities of the compounds. Compounds 5a and 5h showed good activities against cancer-cell lines MDA-MB-435, MDA-MB-231, A549, SiHa, and HeLa. In addition, 5a exhibited quite good anticancer effects on relative above cell lines with 10μM concentration compared with oxaliplatin and gefitinib of the commercial anticancer drugs.     

Background‐free solution boron NMR spectroscopy

The appearance of background signals arising from the NMR probe and tube is a well‐known problem of boron NMR spectroscopy. Background suppression may be achieved by using DEPTH, which increases the signal‐to‐background (S/B) ratio. Although, the quality of such spectra is often adequate, but in the case of rapid relaxation broadened resonances (T₁ < 1 ms), the residual background signals may still hamper the interpretation of the spectra. It was observed that the background signals are practically invisible in solution ¹⁰B NMR. The unusual isotopic effect on the (S/B) ratio was interpreted as an inherent consequence of the integer versus half‐integer spin of ¹⁰B and ¹¹B, respectively. The practicability of ^10/11B NMR was compared for a selected set of boron compounds covering the typical range of (S/B) ratio. The application of ¹¹B is more favourable than ¹⁰B as long as it is possible to achieve the desired spectral quality by using DEPTH. Otherwise, the ‘background‐free’ appearance of ¹⁰B NMR spectra makes ¹⁰B a reasonable alternative of ¹¹B DEPTH. This was found typical for compounds having relaxation broadened resonances. The variable temperature (VT) NMR study of an adduct formation process was also presented here as an example of the advantage of ¹⁰B over ¹¹B. Copyright © 2012 John Wiley & Sons, Ltd.     

Cyanoacetamide Intermediate in Heterocyclic Synthesis: Synthesis and Biological Evaluation of Hitherto New Dioxoisoindoline Heterocyclic Derivatives

Innovative poly‐substituted heterocyclic rings incorporating dioxoisoindoline ( 2 – 25 ) were synthesized through the reaction of dioxoisoindoline derivative 2 as starting compound with various types of reagents. All compounds were characterized by appropriate means of (¹H‐NMR, ¹³C‐NMR, IR, and mass). The prepared compounds were evaluated as antimicrobial agents against Escherichia coli, Staphylococcus aureus, and Candida albicans microorganisms. The tested compounds exhibited low to moderate antibacterial activities and promising results as antifungal agents.     

Unequivocal total assignment of 13C and 1H NMR spectra of some pyrido[1,2‐a]pyrimidine derivatives by 2D‐NMR

We report the total assignments of the ¹³C and ¹H NMR spectra of some 4‐methyl‐2‐oxo‐(2H)‐pyrido[1,2‐a]pyrimidine and 2‐methyl‐4‐oxo‐(4H)‐pyrido[1,2‐a]pyrimidine derivatives. The products were characterized by ¹H and ¹³C NMR and reported data for similar compounds. No comparative data for the two sets of isomeric compounds with respect to ¹³C and ¹H NMR have been reported to date. We made some detailed studies of the 2D NMR spectra of these compounds and observed that assignments made for non‐protonated carbon atoms by us and those reported in the literature for similar compounds need correction. The revised assignments were made on the basis of heteronuclear single quantum correlation (HSQC) and heteronuclear multiple bond correlation (HMBC) techniques. Copyright © 2003 John Wiley & Sons, Ltd.     

Design,synthesis of (Z)‐3‐benzyl‐5‐((1‐phenyl‐3‐(3‐((1‐ substituted phenyl‐1H‐1,2,3‐triazol‐4‐yl)methoxy)phenyl)‐1H‐pyrazol‐4‐yl)methylene)thiazolidine‐2,4‐dione analogues as potential cytotoxic agents

In an attempt to achieve promising cytotoxic agents, a series of new (Z)‐3‐benzyl‐5‐((1‐phenyl‐3‐(3‐((1‐substituted phenyl‐1H‐1,2,3‐triazol‐4‐yl)methoxy)phenyl)‐1H‐pyrazol‐4‐yl)methylene)thiazolidine‐2,4‐diones 10 a‐n were designed, synthesized, and characterized by ¹H NMR, ¹³C NMR, IR, and ESI‐MS techniques. These compounds synthesized from appropriate reaction procedures with better yields. All the novel synthesized compounds 10a‐n were evaluated for their cytotoxic activity against the MCF‐7 cell line (Human breast cancer cell line) at different concentrations of 0.625, 1.25, 2.5, 5, and 10 μM, respectively. The cytotoxic evaluation assay is presented in terms of IC₅₀ values and percentage cell viability reduction compared against standard drug cisplatin. Among all novel synthesized compounds 10a‐n , some of the representative analogues particularly 10g and 10e exhibit remarkable cytotoxic activity with IC₅₀ values 0.454 and 0.586 μM, comparable to that of the standard drug cisplatin, and some analogues 10d , 10f , 10k, and 10m also have shown significant activity.     

1,3-Oxazole-isoniazid hybrids: Synthesis,antitubercular activity,and their docking studies

A series of novel N′-([2-aryl-5-methyl-1,3-oxazole-4-yl]methylene)isonicotino/nicotino hydrazides 10a-l were prepared by the condensation reaction of 2-aryl-5-methyl-1,3-oxazole-4-carbaldehydes 8a-f with the corresponding isonicotino/nicotino hydrazides 9a/9b . The structures of the new compounds were elucidated by various spectroanalytical techniques, including IR, ¹H NMR, ¹³C NMR, elemental (C,H,N), and mass analysis. All the newly prepared INH-1,3-oxazole hybrids were evaluated for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Rv. Among all the synthesized hybrids, compounds 10c and 10i derivatives displayed highest antitubercular activity with minimal inhibitory concentration 1.56 μg/mL. Further, molecular docking studies against the InhA enzyme were carried out to understand the interactions between potent hybrids and the target enzyme. Thus, these kind hybrids have the potentiality for the discovery of new antitubercular agents for deployment in the control and eradication of tuberculosis.     

Synthesis,Characterization, and Antimicrobial Studies of Novel Benzodipyran Analog of Chloramphenicol

A synthesis, characterization, and antimicrobial study of a novel benzodipyran analog of chloramphenicol was carried out. Structure–antimicrobial activity relationship study indicates that benzodipyran analog of chloramphenicol was most active against Gram‐positive bacteria, Staphylococcus aureus, and the fungal strains Rhizoctonia bataticola and Penicillium even at minimum inhibitory concentration 10 µg/mL and showed moderate activity in other bacterial and fungal organisms. All the compounds synthesized during the present investigation were characterized by IR, ¹H NMR, ¹³C NMR, ESI‐MS, and elemental analysis.     

Cycloalkyl substituted <Emphasis Type="Italic">N</Emphasis>-nitrourea derivatives: a convenient synthesis and biological evaluation

A series of N-nitrourea derivatives bearing various cycloalkyl were conveniently obtained via three steps including nitration, carbamic chlorination, and aminolysis reactions. The structures of all newly synthesized compounds were elucidated and confirmed by IR, ¹H NMR, ¹³C NMR, and elemental analysis. The preliminary bioassay indicated that the target compounds exhibited moderate herbicidal activity against Amaranthus albus and Sorghum sudanense. However, some of the title compounds presented high plant growth regulating activity against rice.     

A Greener Approach Synthesis and Docking Studies of Perimidine Derivatives as Potential Anticancer Agents

Microwave solvent‐free technique was employed to the synthesis of series of 2‐(1H‐perimidin‐2(3H)‐ylidene) derivatives, 4‐(1H‐perimidin‐2‐yl)‐1H‐pyrazole‐3‐carboxamides, pyrrolo[1,2‐a]perimidin‐10‐ones, and 8H‐[1,2,4]triazolo[4,3‐a]perimidine. Compared with conventional method, the obvious feature of microwave method is higher in chemical yield, faster reaction rate, and cleaner reaction condition. The structures of the synthesized compounds were confirmed based on their elemental analyses and spectroscopic data (FT‐IR, ¹H‐NMR, ¹⁹F‐NMR, ¹³C‐NMR, and LC‐MS/MS). Some of the synthesized compounds exhibit anticancer potential against the growth of both the human breast (MCF‐7) and the liver carcinoma (HepG2) tumor cells. The most active cytotoxic perimidine derivatives were docked against topoisomerase II to investigate their binding and DNA intercalating activity against the protein crystal structure.     

Synthesis and Stereodynamics of N-Formyl-1,2,3- Selenadiazolopyridines

Abstract

The 4,6-diaryl-6,7-dihydro-[1,2,3]selenadiazolo[5,4-c]pyridine-5(4H)-carbalde hydes were synthesized from 2,6-diarylpiperidin-4-ones and characterized using infrared, ¹H, ¹³C Nuclear Magnetic Resonance (NMR), and mass spectroscopic techniques. On the NMR time scale, the compounds exist in syn and anti isomeric forms. Separate signals were obtained for isomers in the NMR spectra. The compounds’ stereodynamic nature was studied based on the intensity and position of NMR signals.

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